BITUMINOUS COMPOSITION COMPRISING A ROLIN ESTER AND A PLASTICIZING AGENT

Abstract

BITUMINOUS COMPOSITION COMPRISING A ROLIN ESTER AND A PLASTICIZING AGENT The present invention relates to a bituminous composition comprising: a) at least one bitumen base, b) at least one rosin ester, and c) at least one plasticizing agent. Figure for the abstract: None

Description

Title of the invention: BITUMINOUS COMPOSITION COMPRISING A ROSIN ESTER AND A PLASTICIZING AGENT

[0001] The present invention relates to a bituminous composition comprising bitumen, at least one rosin ester, and at least one plasticizing agent. The invention also relates to a method for preparing or using a bituminous composition according to the invention, particularly for road and / or industrial applications.

[0002] Bitumen is the main hydrocarbon constituent used in the field of road construction or civil engineering. It is used, for example, for the production of road surfaces or waterproofing membranes. Bitumen is generally obtained from residues from the atmospheric and / or vacuum distillation of crude oil.

[0003] Oil resources are, however, limited. Indeed, "proven reserves" of oil reached more than 200 billion tonnes of oil equivalent (TOE) in 2018 worldwide, according to experts from British Petroleum (who have been taking stock of the resource since 1980). Although significant, these reserves could only cover 50.2 years of annual consumption at the rate of 2017. These figures are confirmed by the French Alternative Energies and Atomic Energy Commission (CEA) and the International Energy Agency (IEA). It is therefore necessary to limit our oil consumption as much as possible.

[0004] In addition, oil exploitation is responsible for the release of significant quantities of greenhouse gases into the atmosphere, which have a significant impact on global warming. It is therefore necessary to limit our consumption of oil, particularly bitumen, in order to minimize the overall rise in Earth's temperatures.

[0005] In order to maintain and / or improve the characteristics, particularly the mechanical properties, of a conventional bitumen, it is also known to use crosslinked bitumen / polymer compositions in which the bitumen (composed of one or more types of bitumen) is mixed with one or more functional polymers, in particular styrene and butadiene elastomers, these elastomers being chemically crosslinked in situ, possibly with the aid of a coupling or crosslinking agent, for example sulfur or at least one of its precursors. Optimized mechanical characteristics are indeed crucial for road surfacing applications. The carbon footprint associated with these bitumen / However, the carbon footprint of polymers is significantly higher than that of pure bitumen. Indeed, the carbon footprint of pure bitumen is estimated at 0.2 kg of CO2 equivalent per kg of bitumen (estimate provided by the Eurobitume association). The carbon footprint of a polymer, particularly a styrene-butadiene elastomer, is currently estimated at between 2.2 and 3.3 kg of CO2 equivalent per kg of polymer, depending on the process used and plant optimization. Therefore, the need remains for bituminous compositions, especially bitumen / polymer compositions, with a significantly reduced carbon footprint.

[0006] US2011 / 0082240 describes the preparation of bituminous composition incorporating oil rosin oil. This rosin oil is obtained by decarboxylation of rosin resin. It is therefore mainly made up of alcohol.

[0007] There therefore remains a need for bituminous compositions whose content of material(s) of fossil origin, in particular derived from petroleum, is reduced compared to the compositions of the prior art.

[0008] In particular, there remains a need for bituminous compositions having mechanical properties, in particular elastic properties, which are improved compared to the polymer-free compositions of the prior art, and whose content of material(s) of fossil origin, in particular derived from petroleum, is reduced compared to the compositions of the prior art.

[0009] Even more particularly, there remains a need for bitumen / polymer compositions (possibly crosslinked) whose content of material(s) of fossil origin, in particular derived from petroleum, is reduced compared to the compositions of the prior art.

[0010] There also remains a need to provide bituminous compositions with a reduced carbon footprint, compared to the compositions of the prior art.

[0011] In particular, there remains a need for bituminous compositions with improved mechanical properties, especially elastic ones, compared to polymer-free compositions of the prior art, and with a reduced carbon footprint compared to compositions of the prior art.

[0012] Even more specifically, there remains a need for bitumen / polymer compositions (possibly crosslinked) with a reduced carbon footprint, compared to prior art compositions.

[0013] In its previous work, the Applicant discovered that it was possible to reduce the content of fossil-based material(s) by incorporating rosin ester(s) into a bituminous composition, particularly a bitumen / polymer composition. Specifically, the Applicant discovered that it was possible to reduce the carbon footprint of prior art bituminous compositions, particularly bitumen / polymer compositions, by incorporating rosin ester(s).

[0014] The compositions obtained exhibit entirely satisfactory properties both for their application as road binders and for the preparation of membranes. The compositions comply with all the required specifications.

[0015] The Applicant has however found that the incorporation of rosin esters has the consequence of degrading certain properties of the bituminous composition. In particular, the Applicant has found that the incorporation of the esters results in a slight reduction in the penetrability at 25°C of the composition, as well as a drop in the mechanical properties of the composition, in particular its maximum elongation, compared to a bituminous composition free of rosin esters.

[0016] There therefore remains a need to provide bituminous compositions with a reduced carbon footprint, thanks to the incorporation of rosin ester(s), and with improved properties, particularly in terms of penetrability and / or elastic properties. In particular, there remains a need to provide bituminous compositions based on rosin ester(s) that have equivalent, or even improved, properties compared to bituminous compositions free of rosin esters, particularly in terms of penetrability and elastic properties.

[0017] In continuation of its work, the Applicant discovered that it was possible to compensate for the deterioration of the mechanical properties of the bituminous composition caused by the incorporation of rosin esters by the addition of one or more plasticizing agents. In particular, the Applicant discovered that the incorporation, in a bituminous composition comprising rosin ester(s), of one or more plasticizing agents made it possible to improve certain of the mechanical properties of the composition, notably by increasing the penetration at 25°C and / or the maximum elongation of the composition. Summary of the invention

[0018] The invention relates firstly to a bituminous composition comprising:

[0019] - at least one bitumen base,

[0020] - at least one rosin ester, and

[0021] - at least one plasticizing agent.

[0022] Preferably, the plasticizing agent is chosen from:

[0023] a) tall oil derivatives,

[0024] b) plastic pyrolysis oils,

[0025] c) triglycerides

[0026] d) mixtures of a) and / or b) and / or c).

[0027] Preferably, the rosin ester is chosen from among the pentaerythritol esters of natural rosins, pentaerythritol esters of hydrogenated rosins and any mixture thereof, more preferably pentaerythritol esters of natural rosins.

[0028] Advantageously, the rosin ester has a melting point, measured by differential scanning calorimetry, ranging from 40°C to 150°C, more preferably ranging from 50°C to 120°C.

[0029] Preferably, the rosin ester has an acidity level, measured according to the ASTM D465 method, of less than or equal to 250 mg KOH / g, more preferably less than or equal to 100 mg KOH / g.

[0030] Advantageously, the composition of the invention has a rosin ester(s) content ranging from 0.1% to 50% by mass, preferably from 0.5% to 30% by mass, preferably from 1% to 15% by mass, relative to the total mass of the bituminous composition.

[0031] According to one embodiment, the composition of the invention further comprises at least one elastomer, preferably chosen from copolymers of an aromatic monovinyl hydrocarbon and a conjugated diene.

[0032] Preferably, according to this embodiment, the composition of the invention is a crosslinked bitumen / polymer composition, obtained by crosslinking, in particular chemical or thermal.

[0033] The invention also relates to a method for preparing a bituminous composition according to the invention, this method comprising:

[0034] 1) bringing the following components into contact:

[0035] - at least one bitumen base,

[0036] - at least one rosin ester, and

[0037] - at least one plasticizing agent

[0038] 2) the mixing of the components.

[0039] Preferably, the mixing of the components is carried out under heating and stirring, preferably at a temperature ranging from 90°C to 230°C, more preferably from 120°C to 200°C, even more preferably from 150°C to 180°C.

[0040] The invention further relates to the use of a bituminous composition of the invention, to prepare a surface coating, a hot mix asphalt, a cold mix asphalt, a cold poured asphalt, an emulsion gravel or a wearing course, said binder being associated with aggregates and / or recycled millings.

[0041] The invention also relates to a bituminous coating comprising a bituminous composition of the invention, mixed with aggregates and / or recycled millings, and optionally mineral and / or synthetic fillers.

[0042] The invention also relates to an asphalt comprising a bituminous composition according to the invention, mixed with mineral and / or syn- fillers thematic.

[0043] The invention also relates to a waterproofing coating, preferably a membrane or an impregnation layer, comprising a bituminous composition according to the invention.

[0044] The invention further relates to the use in a bituminous composition, in particular in a bitumen / polymer composition possibly crosslinked, of the association of at least one rosin ester and at least one plasticizing agent, to reduce the content of compound(s) of fossil origin in said composition.

[0045] The invention finally relates to the use in a bituminous composition, in particular in a bitumen / polymer composition possibly crosslinked, of the association of at least one rosin ester and at least one plasticizing agent, to reduce the carbon footprint of said composition. Detailed description of the invention

[0046] In the following description, and unless explicitly stated otherwise, the quantities of the different components present in a bituminous composition according to the invention are given as % mass, relative to the total mass of the composition (hereinafter referred to as % w / w).

[0047] Similarly, and unless explicitly stated otherwise, the standards mentioned in the rest of the description correspond to the standard in force on October 1, 2023.

[0048] The invention relates firstly to a bituminous composition comprising:

[0049] - at least one bitumen base,

[0050] - at least one rosin ester, and

[0051] - at least one plasticizing agent. Bitumen base

[0052] The bitumen(s) used to prepare a bitumen / polymer composition according to the invention are called “bitumen base”.

[0053] Among the bitumens that can be used according to the invention, we can first mention bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt, or oil sands, and bitumens obtained from crude oil refining. Within the scope of the invention, the bitumen(s) used are advantageously chosen from among bitumens obtained from crude oil refining, in particular bitumens containing asphaltenes or pitches. The bitumens can be obtained by conventional bitumen manufacturing processes in refineries, in particular by direct distillation and / or vacuum distillation of petroleum. These bitumens can optionally be viscoreduced and / or deasphalted and / or air rectified. It is common practice to carry out vacuum distillation of atmospheric residues from the atmospheric distillation of crude oil. This manufacturing process corresponds, by Consequently, to the succession of atmospheric distillation and vacuum distillation, the feedstock feeding the vacuum distillation corresponding to the atmospheric residues. These vacuum residues from the vacuum distillation tower can also be used as bitumens. It is also common to inject air into a feedstock usually composed of distillates and heavy products from the vacuum distillation of atmospheric residues from the distillation of oil. This process makes it possible to obtain a blown, or semi-blown, or oxidized, or air-rectified, or partially air-rectified bitumen.

[0054] Different bitumens obtained by refining processes can be combined in the compositions according to the invention to obtain the best compromise in terms of technical performance. In conventional processes for blending different bitumens, the mixture is blended at temperatures between 100°C and 200°C, preferably between 140°C and 200°C, and with agitation for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, and more preferably between 1 and 6 hours. The temperature and duration of heating vary according to the quantity of bitumen used and are defined by standard NF EN 12594. Blown bitumens can be manufactured in a blowing unit by passing a flow of air and / or oxygen through a starting bitumen or mixture of bitumens. This operation can be carried out in the presence of an oxidation catalyst, for example, phosphoric acid.

[0055] Generally, blowing is carried out at high temperatures, of the order of

[0056] 200 to 300°C, for relatively long periods of time typically between 30 minutes and 2 hours, continuously or in batches. The blowing time and temperature are adjusted according to the desired properties of the blown bitumen and the quality of the starting bitumen.

[0057] Among the bitumens that can be used according to the invention, mention may also be made of recycling bitumens.

[0058] Bitumens can be hard grade bitumens (such as grades 10 / 20 and 20 / 30) or soft grade bitumens (such as grade 160 / 220) as defined by standard EN 12591.

[0059] The invention is particularly suitable for cases where the bitumen base consists of a hard grade bitumen or a mixture of hard grade bitumens, in particular chosen from bitumens of grade 35 / 50, 20 / 30 and 10 / 20.

[0060] The bitumen bases usable within the scope of the invention preferably have a penetrability, measured at 25°C according to standard EN 1426, of 5 to 330 1 / 10 mm, preferably between 10 and 220 1 / 10 mm, more preferably between 10 and 120 1 / 10 mm. As is well known, the so-called "needle penetration" measurement is carried out using a standardized test according to NF EN 1426 at 25°C (P25). This penetrability characteristic is expressed in tenths of a millimeter (dmm or 1 / 10 mm). The needle penetration, measured at 25°C, according to the standardized test NF EN 1426, represents the measurement of the penetration into a sample of bitumen, after a time of 5 seconds, of a needle whose weight with its support is 100 g.

[0061] Preferably, the bituminous composition according to the invention comprises at least 40% by mass of bitumen, relative to the total mass of the bituminous composition, preferably at least 50% by mass, more preferably at least 60% by mass, advantageously at least 70% by mass, more advantageously at least 80% by mass, even more advantageously at least 85% by mass.

[0062] Advantageously, the bituminous composition according to the invention comprises from 40% to 99.9% by mass, relative to the total bituminous composition, preferably from 50% to 99% by mass, more preferably from 60% to 95% by mass, even more preferably from 70% to 95% by mass, advantageously from 75% to 95% by mass, and more advantageously from 80% to 95% by mass of rosin ester

[0063] The bituminous composition according to the invention also comprises at least one rosin ester.

[0064] By "rosin ester" is meant the product of the reaction between products derived from rosin, in particular abietic acid, and an alcohol.

[0065] Rosin (or "Rosin oil" in English) is a solid residue obtained after the distillation of various elements such as turpentine or oleoresin harvested from resinous trees such as pines. Rosins can be natural or they can be chemically transformed, in which case we speak of modified natural rosins.

[0066] Natural rosin is composed of 90% of a mixture of organic acids from the diterpene family called resin acids, notably abietic acid. These resin acids are isomers. The proportion of the different resin acids in rosin varies depending on the species of pine from which it was obtained.

[0067] Among the natural rosins, mention may be made of gem and wood rosins, in particular pine, and / or tall oil. These natural rosins can be taken alone or in a mixture.

[0068] Among the modified rosins, mention may be made of hydrogenated rosins, disproportionated rosins, polymerized rosins and / or maleized rosins. These modified natural rosins may be taken alone or in a mixture, and undergo one or more disproportionation, polymerization and / or maleization treatments.

[0069] Preferably, the rosin used is a natural rosin composed mainly of resin acids, preferably chosen from: abietic acid, pimaric acid, their derivatives, in particular the dimers and / or trimers thereof, and any of their mixtures.

[0070] Preferably, the rosin of the invention has a hydrocarbon chain comprising from 18 to 300 carbon atoms.

[0071] More preferably, the hydrocarbon chain of the rosin of the invention comprises from 20 to 290 carbon atoms, even more preferably from 25 to 280 carbon atoms, advantageously from 36 to 280 carbon atoms.

[0072] Preferably, the ratio between the number of oxygen atoms and the number of carbon atoms present in the rosin of the invention is 1:100 to 1:5, more preferably from 1:50 to 1:10, even more preferably from 1:30 to 1:20.

[0073] The alcohol may be primary, secondary or tertiary. In particular, it may be a monol, a diol or a polyol. The alcohol may also come from polyethers such as triethylene glycol or polyethylene glycols.

[0074] Preferably, the alcohol is chosen from compounds having one or more hydrocarbon chains chosen, independently, from linear, branched, cyclic or aromatic hydrocarbon chains, and comprising one or more alcohol functions.

[0075] More preferably, the alcohol is chosen from: ethanol, 1-propanol, isobutyl alcohol, 2-ethylhexanol, octanol, isodecyl alcohol, benzyl alcohol, cyclohexanol, ethylene glycol monobutyl ether, ethylene glycol, propylene glycol, diethylene glycol, resorcinol, triethylene glycol, neopentyl glycol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, sorbitol, sucrose and the like, and any of their mixtures.

[0076] Preferably, the alcohol chosen is from glycerol, pentaerythritol and any of their mixtures.

[0077] Advantageously, the alcohol chosen is pentaerythritol.

[0078] The ester used according to the invention may be a mono-, a di-, or a triester. It may be a mixture of mono-, di- and triester.

[0079] Among the rosin esters, mention may be made of methyl esters of natural rosins, methyl esters of hydrogenated rosins, esters of glycerol and natural rosins, esters of glycerol and hydrogenated rosins, esters of glycerol and disproportionated rosins, esters of glycerol and polymerized rosins, esters of glycerol and maleated rosins, pentaerythritol esters of natural rosins and pentaerythritol esters of hydrogenated rosins. These rosin esters may be taken alone or as a mixture and come from rosins having undergone one or more disproportionation, polymerization and / or maleization treatments.

[0080] Preferably, the rosin ester of the invention is chosen from pentaerythritol esters of natural rosins, pentaerythritol esters of hydrogenated rosins, and any mixture thereof, more advantageously from the esters pentaerythritol and natural rosins.

[0081] According to a preferred embodiment, the rosin ester of the invention is chosen from pentaerythritol esters of tall oil rosins.

[0082] For further information on the rosin esters of plant origin which can be used according to the invention, reference may be made to article K340 by Bernard Delmond published in “Techniques de l'ingénieur”.

[0083] The rosin esters used according to the invention are characterized by their melting point, measured by differential scanning calorimetry. Preferably, the rosin ester according to the invention has a melting point of between 30°C and 180°C, more preferably of between 40°C and 150°C, typically between 50°C and 120°C.

[0084] The rosin esters used according to the invention are characterized by their softening temperature, determined according to standard EN 1427. Preferably, the resin of plant origin has a softening temperature, determined according to method AQCM 003, of between 60°C and 200°C, preferably between 70°C and 150°C, more preferably between 80°C and 110°C.

[0085] Preferably, the resin of plant origin has a glass transition temperature, measured according to the AQCM 218 method, of between 10°C and 80°C, preferably between 20°C and 60°C, more preferably between 40°C and 50°C.

[0086] The rosin esters used in the invention are also characterized by their acidity index, determined according to the ASTM D465 method.

[0087] Preferably, the rosin ester has an acidity index, determined according to the ASTM D465 method, of less than or equal to 250 mg KOH / g, more preferably less than or equal to 100 mg KOH / g, even more preferably less than or equal to 50 mg KOH / g.

[0088] Advantageously, the rosin ester typically has an acidity index, determined according to the ASTM D465 method, of less than 8 mg KOH / g.

[0089] Preferably, the rosin ester has an acidity index, determined according to the ASTM D465 method, of between 0.1 and 8 mg KOH / g, preferably between 0.2 and 7 mg KOH / g, more preferably between 0.5 mg and 6 mg KOH / g.

[0090] Advantageously, the rosin ester has an acidity index, determined according to the ASTM D465 method, of less than or equal to 5 mg KOH / g.

[0091] Preferably, the rosin ester has a Gardner color index, determined according to ASTM D6166, of less than or equal to 10, more preferably less than or equal to 5, even more preferably less than or equal to 1, typically 0.9.

[0092] The rosin esters used according to the invention are characterized by their Brookfield viscosity, determined according to the AQCM 004 method.

[0093] Preferably, the resin of vegetable origin has a Brookfield viscosity at 125°C, measured according to the AQCM 004 method, greater than or equal to 5,000 mPa.s, preferably between 7,500 mPa.s and 15,000 mPa.s, more preferably between 10,000 mPa.s and 11,000 mPa.s.

[0094] Preferably, the resin of plant origin has a Brookfield viscosity at 150°C, measured according to the AQCM 004 method, greater than or equal to 500 mPa.s, preferably between 750 mPa.s and 1500 mPa.s, more preferably between 900 mPa.s and 1000 mPa.s.

[0095] Preferably, the resin of plant origin has a Brookfield viscosity at 177°C, measured according to the AQCM 004 method, greater than or equal to 80 mPa.s, preferably between 100 mPa.s and 500 mPa.s, more preferably between 150 mPa.s and 200 mPa.s.

[0096] For example, a rosin ester usable in the bituminous compositions according to the invention may be a product marketed by the company KRATON under the name: SYLVALITE® 2100 Rosin Ester.

[0097] Preferably, the bituminous composition according to the invention has a content of rosin ester(s) ranging from 0.1% to 50% by mass, preferably from 0.5% to 30% by mass, preferably from 1% to 15% by mass, relative to the total mass of the bituminous composition. Plasticizing agent

[0098] The bituminous composition according to the invention further comprises at least one plasticizing agent.

[0099] For the purposes of this invention, "plasticizing agent" means a compound capable of reducing the Young's modulus and the glass transition temperature of a material, in order to improve its cold properties, limit its brittleness, and increase its elongation at break.

[0100] The plasticizing agent is not specifically limited provided that it possesses the qualities required for the bituminous compositions of the invention. In particular, any plasticizing agent known to those skilled in the art and suitable for use in bitumens, especially bitumen / polymer compositions, may be used.

[0101] According to a preferred embodiment, the plasticizing agent is selected from:

[0102] a) tall oil derivatives,

[0103] b) plastic pyrolysis oils,

[0104] c) triglycerides, and

[0105] d) mixtures of a) and / or b) and / or c).

[0106] Preferably, the bituminous composition according to the invention has a plasticizing agent(s) content ranging from 0.1% to 30% by mass, preferably from 1% to 20% by mass, preferably from 2.5% to 10% by mass, relative to the total mass of the composition.

[0107] Preferably, the rosin ester(s) and the plasticizing agent are present in the bituminous composition of the invention in a mass ratio of 10:1 to 1:10, more preferably from 5:1 to 1:5, even more preferably from 2:1 to 1:2, typically in a ratio of 1:1. a) Tall oil derivatives

[0108] According to a first embodiment, the plasticizing agent is chosen from tall oil derivatives.

[0109] Crude tall oil (or CTO) is a by-product of the wood-to-paper pulp process, also known as the Kraft process. Distillation of crude tall oil yields a volatile, highly saturated fraction of long-chain fatty acids (primarily palmitic acid), called "tall oil heads." The next cut is tall oil fatty acids (or TOFA). This TOFA cut consists primarily of C18 and C20 fatty acids with varying degrees of unsaturation (e.g., oleic acid, linoleic acid, linolenic acid, and various isomers thereof). Another cut, known as distilled tall oil (or DTO for "Distilled Tall OU" in English), is a mixture consisting mainly of tall oil fatty acids and a smaller proportion of tall oil rosin.Tall oil rosin (TOR), as isolated next, consists largely of a C19-C20 tricyclic monocarboxylic acid. The lower cut from the distillation is known as tall oil pitch (or simply pitch).

[0110] Preferably, according to this embodiment, the plasticizing agent is obtained directly from tall oil by simple distillation.

[0111] More preferably, the plasticizing agent is chosen from: crude tall oil, fractions of crude tall oil and mixtures of different fractions of tall oil.

[0112] Even more preferably, according to this embodiment, the plasticizing agent is chosen from "tall oil heads", tall oil fatty acids (or TOFA for "Tall OR Fatty Acids" in English), distilled tall oil (or DTO for "Distilled Tall Oil" in English), tall oil rosin (or TOR for "Tall Oil Rosin") and tall oil pitch or tall oil pitch (in English "tall oilpitch" or simply "pitch").

[0113] Even more preferably, the plasticizing agent is chosen from tall oil pitch or tall oil pitch (in English “tall oil pitch” or simply “pitch”).

[0114] Tall oil pitch, referenced under CAS No. 8016-81-7, is in the form of a complex mixture comprising mainly fatty acids such as palmitic acid, linoleic acid and oleic acid; fatty acid esters; re- sinic acids such as abietic acid and its isomers, pimaric acid, iso-pimaric acid and sandaracopimaric acid; resin acid esters; diterpene alcohols; fatty alcohols and sterols.

[0115] Preferably, the tall oil pitch comprises:

[0116] - up to 30% by mass of free fatty acids,

[0117] - from 15% to 20% by mass of diglycerides,

[0118] - from 50% to 60% by mass of triglycerides, and

[0119] - from 10% to 15% by mass of sterols,

[0120] relative to the total mass of the pitch.

[0121] Preferably, the tall oil pitch has an iodine index, measured according to standard NF EN ISO 3961, less than or equal to 100 g of I2 / 100 g of pitch, more preferably ranging from 70 to 100 g of I2 / 100 g of pitch, advantageously from 75 to 95 g of I2 / 100 g of pitch.

[0122] Preferably, tall oil pitch has an acid value, measured according to standard NF EN ISO 660, less than or equal to 45 g of KOH / g of pitch, more preferably ranging from 10 to 40 g of KOH / g of pitch, advantageously from 10 to 35 g of KOH / g of pitch.

[0123] Preferably, according to this embodiment, at least 50% by mass of the plasticizing agent consists of tall oil derivatives, more preferably at least 60% by mass, more preferably at least 75% by mass, advantageously at least 80% by mass, more advantageously at least 90% by mass, typically at least 95% by mass.

[0124] More preferably, according to this embodiment, the plasticizing agent consists of tall oil derivatives. b) plastic pyrolysis oils

[0125] According to a second embodiment, the plasticizing agent is chosen from plastic pyrolysis oils.

[0126] For the purposes of this invention, "plastic pyrolysis oil" means a hydrocarbon product obtained by thermal conversion, in particular by pyrolysis, of plastics.

[0127] High-temperature pyrolysis processes make it possible to transform plastic waste into several products in varying proportions depending on the nature of the waste used: an oil, a gas mixture, coke.

[0128] Common industrial methods of recycling hydrocarbons from plastic include thermal conversion liquefaction of plastic waste that might otherwise have ended up in a landfill or incinerator, followed by a purification step including hydrotreatment and the removal of contaminants using a variety of purification processes such as distillation.

[0129] Liquefaction of plastic waste can be achieved in particular by pyrolysis or by hydrothermal treatment. The thermal conversion step transforms the plastics and most of their additives and contaminants into gaseous chemicals, while most of the non-volatile contaminants or additives are found in the solid by-product, the coals or the ash. In principle, all types of plastic waste can be converted. However, a preliminary step of sorting non-organic waste is desirable. Purification of the output material is also necessary because several hetero-elements (i.e. elements other than carbon, hydrogen or oxygen) can be volatilized.

[0130] Plastic waste is a complex and heterogeneous material, due to several factors. First of all, plastic as a material refers to many different polymers with different chemical properties that need to be separated from each other before recycling. The main polymers present in plastic from municipal solid waste are polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), and polystyrene (PS). Other polymers mainly include polyurethanes, polyamides (PA), polycarbonates, polyethers, and polyesters other than PET. In addition, many additives different from the basic polymers are introduced during the production phase to adjust or improve the properties of the plastic or to meet specific requirements.These include functional additives (stabilizers, antistatic agents, flame retardants, plasticizers, lubricants, sliding agents, curing agents, foaming agents, biocides, antioxidants, etc.), colorants and pigments, fillers (e.g., glass fibers, talc, carbon fibers, carbon nanotubes), commonly used in plastic packaging, as well as additives such as flame retardants, frequently used in plastics for electronics. In addition, several metallic compounds are intentionally added during plastic production (often in the form of oxides, carbonates, acids, etc.). Additives containing heteroatoms other than metals are also used in plastics manufacturing, for example, halogens such as bromine in flame retardants, plasticizers, stabilizers, etc.

[0131] Silicone polymers, which are organic materials containing silicon, are often used in plastic formulations. Due to their surface characteristics, the applications of silicones range from silicone rubbers, used as sealants for joints, to silicone surfactants for cosmetic products, while they are increasingly used in the plastics sector, as process-enhancing additives (manufacturing aids), and for the modification of polymers.

[0132] In addition to these heteroelements, used plastic waste may have been contaminated during its lifetime by residues of liquids with which it has been in contact (beverages, personal care products, etc.) and food, which can also contaminate the plastic. Finally, some plastic waste may be present in the form of partially decomposed waste, such as partially burned plastic.

[0133] Finally, since plastics are contaminated with oxygenated compounds, plastic oils resulting from pyrolysis liquefaction may also contain oxygenated compounds such as aldehydes or ketones.

[0134] The oil resulting from the pyrolysis of the plastic can then be separated into several fractions by all types of separation processes known per se:

[0135] • The light naphtha cut with a distillation range between 50 and 200°C and a density between 720 Kg / m3 and 750 Kg / m3;

[0136] • The average diesel cut with a distillation interval between 200°C and 300°C and a density between 750 Kg / m3 and 800 Kg / m3;

[0137] • The heavy cut type VGO (“Vaccum Gasoil” in English) with an interval of distillation between 300°C and 450°C and a density between 800 Kg / m3 and 840 Kg / m3;

[0138] • A very heavy cut type VR (Visco-Reduced) with an initial boiling point of at least 450°C and a density between 840 Kg / m3 and 870 Kg / m3.

[0139] Preferably, the plasticizing agent is chosen from light cut naphtha type, medium cut diesel type, heavy cut VGO type, very heavy cut VR type and any of their mixtures.

[0140] Preferably, according to this second embodiment, at least 50% by mass of the plasticizing agent consists of plastic pyrolysis oils, more preferably at least 60% by mass, more preferably at least 75% by mass, advantageously at least 80% by mass, more advantageously at least 90% by mass, typically at least 95% by mass.

[0141] More preferably, according to this third embodiment, the plasticizing agent consists of pyrolysis oils of plastics, c) triglycerides

[0142] According to a third embodiment, the plasticizing agent is chosen from triglycerides.

[0143] By "triglycerides", we mean, in the sense of the invention, glycerides, that is to say, esters of glycerol, whose three alcohol functions have been esterified.

[0144] Preferably, the triglycerides are chosen from the compounds of the following formula (I):

[0145] in which RI, R2 and R3 represent, independently, a hydrocarbon chain, linear or branched, saturated or unsaturated, comprising from 1 to 300 carbon atoms, and optionally one or more heteroatoms, preferably chosen from O and N.

[0146] Preferably, each of the groups RI, R2 and R3 comprises, independently, from 0 to 3 unsaturations.

[0147] Preferably, the groups RI, R2 and R3 represent, independently, a hydrocarbon chain in CrCioo, more preferably in C2-C50, even more preferably in C4-C36, optionally substituted by one or more heteroatoms, preferably chosen from O and N.

[0148] More preferably, the triglycerides of the invention are chosen from fatty acid triglycerides.

[0149] Preferably, the fatty acids are selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, ricinoleic acid, behenic acid, lignoceric acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, trans-vaccenic acid, linoleic acid, linoaidic acid, α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid, clupanodonic acid, docosahexaenoic acid and mixtures thereof.

[0150] More preferably, the fatty acids are chosen from palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, α-linolenic acid and mixtures thereof.

[0151] Even more preferably, the fatty acids are in the form of a mixture of palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, and α-linolenic acid.

[0152] Advantageously, fatty acids consist of a mixture comprising:

[0153] - 0.7% to 1.3% by mass of palmitic acid,

[0154] - from 0.9% to 1.2% by mass of stearic acid,

[0155] - from 2.8% to 5.5% by mass of oleic acid,

[0156] - from 84.2% to 94% by mass of ricinoleic acid,

[0157] - from 4.2% to 7.3% by mass of linoleic acid, and

[0158] - 0.2% to 0.5% by mass of α-linolenic acid,

[0159] relative to the total mass of fatty acids present in the triglycerides of the invention, in esterified form.

[0160] Triglycerides suitable for the invention are notably present in animal fats, vegetable oils or dairy products.

[0161] Preferably, the triglycerides of the invention are of vegetable origin.

[0162] More preferably, the triglycerides of the invention are derived from castor oil.

[0163] Preferably, according to this third embodiment, at least 50% by mass of the plasticizing agent consists of triglycerides, more preferably at least 60% by mass, more preferably at least 75% by mass, advantageously at least 80% by mass, more advantageously at least 90% by mass, typically at least 95% by mass.

[0164] More preferably, according to this third embodiment, the plasticizing agent consists of triglycerides, d) mixtures

[0165] The plasticizing agent of the invention may also consist of a mixture of the different compounds defined above. In particular, the plasticizing agent may consist of a mixture of tall oil derivatives and biomass pyrolysis oils, a mixture of tall oil derivatives and triglycerides, a mixture of plastic pyrolysis oils and triglycerides or a mixture of tall oil derivatives, plastic pyrolysis oils and triglycerides. Elastomer

[0166] According to one embodiment, the composition according to the invention further comprises at least one elastomer.

[0167] The elastomer is not particularly limited provided that it has the qualities required for the bituminous compositions of the invention.

[0168] Such elastomers are well known in the art and are generally rubbery polymers. In a preferred embodiment, the elastomer comprises styrene butadiene styrene (SBS), hydrogenated SBS, styrene isoprene styrene (SIS), styrene ethylene butadiene styrene (SEBS) and / or polyisobutadiene (PIB).

[0169] Preferably, the elastomer is typically chosen from copolymers of an aromatic monovinyl hydrocarbon and a conjugated diene

[0170] Preferably, the elastomer is chosen from block copolymers of formula SBS, in which:

[0171] - each S, which may be identical or different, independently represents a block based on aromatic monovinyl hydrocarbon monomers,

[0172] - B represents a butadiene monomer-based block, said block B comprising pendant vinyl groups.

[0173] For the purposes of this invention, "block" means a polymer chain obtained by the polymerization of one or more monomers of the same chemical nature. A block advantageously consists of the repetition of the same monomer.

[0174] In said block copolymers of formula SBS, the S blocks together represent at least 15% by mole of the total number of moles of monomeric units of the block copolymer. These block copolymers have a weight-average molecular mass ranging from 40,000 to 500,000 g / mol and have a content of pendant vinyl groups contained in block B that is greater than or equal to 20% by mole, relative to the total number of moles of monomeric units of the block copolymer. These copolymers may hereafter be referred to more simply as SBS elastomer. In general, the two S blocks of the SBS thermocurable elastomer are identical.

[0175] In the context of the invention, butadiene refers to 1,3-butadiene, which is a conjugated diene. When butadiene, or more generally a conjugated diene, is polymerized via a 1,2-addition mechanism, the result is a vinyl group (also called a vinylic group) that hangs from the polymer backbone. The hanging vinylic groups of the SBS block copolymer therefore correspond to the 1,2-addition polymerization of the conjugated diene monomers, and in particular the major butadiene monomers, within block B. The motifs obtained by the polymerization of butadiene via a 1,2-addition mechanism or via a 1,4-addition mechanism have the same molar mass.

[0176] In particular, the aromatic monovinyl hydrocarbon monomer(s) present in the S blocks of the SBS thermocrosslinkable elastomer are selected from styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene or mixtures thereof. The preferred monovinyl aromatic hydrocarbon monomer according to the present invention is styrene, which is used, for the constitution of the S blocks as the sole monomer, or as the major monomer in mixtures with minor proportions of one or more other monomers such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene, namely, in proportions of at most 10% by mass, relative to the totality of the monovinyl aromatic hydrocarbon monomers present in said S blocks.The use of styrene as the sole monomer is particularly preferred in the present invention for the constitution of the S blocks of the SBS elastomer. Thus, the monovinylaromatic hydrocarbon monomers from which the S blocks of the thermocrosslinkable block SBS copolymers are derived. may be, independently, any monovinylaromatic hydrocarbon monomer as previously described and are preferably styrene.

[0177] The block B based on butadiene monomers entering into the composition of the mentioned block copolymers SBS is, preferably, solely composed of butadiene monomers, or of a mixture of butadiene comprising minor proportions of one or more other structurally related conjugated dienes, and in particular chosen from isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene, in particular representing at most 10% by mass, relative to the totality of the conjugated dienes present in the block B. Preferably, the monomers constituting the block B are exclusively butadiene monomers.

[0178] The SBS thermocrosslinkable block elastomer used in the context of the invention has a weight-average molecular mass Mw of 40,000 to 500,000 g / mol. Preferably, the SBS thermocrosslinkable block elastomer has a weight-average molecular mass Mw of less than or equal to 400,000 g / mol, more preferably less than or equal to 250,000 g / mol, even more preferably less than or equal to 200,000 g / mol and advantageously less than or equal to 150,000 g / mol.

[0179] Preferably, the SBS block copolymer used in the context of the invention has a weight-average molecular weight Mw greater than or equal to 50,000 g / mol, more preferably greater than or equal to 65,000 g / mol, even more preferably greater than or equal to 75,000 g / mol, and advantageously greater than or equal to 100,000 g / mol. According to particular embodiments, the SBS block copolymer has a weight-average molecular weight Mw in any range corresponding to the maximum and minimum values ​​mentioned above, and advantageously in the range from 100,000 to 150,000 g / mol.

[0180] As previously stated, the SBS block copolymer used in the invention has a content of pendant vinyl groups greater than or equal to 5% by mole, relative to the total number of moles of monomeric units of the copolymer. This vinyl content, determined by coupling 13C NMR (carbon nuclear magnetic resonance) and 1H NMR (proton nuclear magnetic resonance) spectroscopy techniques, allows the polymer to be characterized.

[0181] Preferably, the SBS block copolymer has a content of pendant vinyl groups greater than or equal to 5% by moles, relative to the total number of moles of monomeric units of the SBS copolymer, preferably greater than or equal to 10%.

[0182] According to one embodiment, the SBS block copolymer preferably has a content of pendant vinyl groups less than or equal to 50% by mole, relative to the total number of moles of monomeric units of the SBS copolymer, more preferably less than or equal to 40% by mole, even more preferably less than or equal to 30% by moles, typically less than or equal to 20% by moles.

[0183] Advantageously according to this first embodiment, the SBS block copolymer has a content of pendant vinyl groups in any range corresponding to the maximum and minimum values ​​mentioned above, and advantageously in the range from 5% to 20% by moles.

[0184] According to a second embodiment, the SBS block copolymer used according to the invention preferably has a content of pendant vinyl groups greater than or equal to 25% by moles, relative to the total number of moles of monomeric units of the SBS copolymer, more preferably greater than or equal to 30% by moles.

[0185] Preferably, according to this second embodiment, the SBS block copolymer used according to the invention has, preferably, a content of pendant vinyl groups less than or equal to 50% by mole, relative to the total number of moles of monomeric units of the SBS copolymer, more preferably less than or equal to 45% by mole. Advantageously, according to this second embodiment, the SBS block copolymer has a content of pendant vinyl groups in any range corresponding to the maximum and minimum values ​​mentioned above, and advantageously in the range of 35% to 45% by mole.

[0186] Preferably, the pendant vinyl groups are distributed along block B of the SBS polymer in a statistical manner. This characteristic results directly from the process implemented for the synthesis of the copolymer.

[0187] The number of moles of monomeric units of the S blocks present in the SBS block copolymer represents, together, at least 15% of the total number of moles of monomeric units of the SBS copolymer, preferably at least 16% in moles.

[0188] Preferably, the number of moles of monomeric units of the S-blocks of the SBS polymer represents, together, from 15% to 50% by moles, relative to the total number of moles of monomeric units of the SBS block copolymer, more preferably from 16% to 30% by moles, even more preferably from 16% to 25% by moles, and advantageously from 16% to 20% by moles. The number of moles of monomeric units of the S-blocks of the SBS polymer can be determined by 13C NMR spectroscopy (NMR Resonance

[0189] Nuclear Magnetic of carbon).

[0190] Preferably, the content of aromatic monovinyl hydrocarbon monomer (advantageously styrene) of the SBS block copolymer, determined by 13C NMR (Nuclear Magnetic Resonance of carbon) spectroscopy, is greater than or equal to 25% by mass, more preferably greater than or equal to 28% by mass, even more preferably greater than or equal to 30% by mass, relative to the total mass of the block copolymer of formula SBS.

[0191] Preferably, the monovinyl aromatic hydrocarbon monomer content (advantageously styrene) of the SBS block copolymer, determined by 13C NMR spectroscopy (Nuclear Magnetic Resonance of carbon), ranges from 25% to 40% by mass, even more advantageously from 28% to 35% by mass, relative to the total mass of the SBS block copolymer.

[0192] Advantageously, SBS block elastomers are in an essentially non-hydrogenated form.

[0193] According to a particular embodiment, the block copolymer of formula SBS is obtained by coupling two block copolymers of formula S-B' in which blocks S and B' are selected to obtain an SBS block copolymer. Block B may therefore include a residue of a coupling agent, well known in the field concerned. Examples of difunctional coupling agents include dibromoethane, diethyl adipate, divinylbenzene, dimethyldichlorosilane, and methyl dichlorosilane.

[0194] Preferably, according to this particular embodiment, the efficiency of the coupling of the two block copolymers of formula S-B', measured by gel permeation chromatography, is greater than or equal to 50%, more preferably greater than or equal to 75%, even more preferably greater than or equal to 90% and advantageously greater than or equal to 95%.

[0195] Examples of SBS block copolymers usable in compositions according to the invention, as well as their preparation processes, are described in particular in US patent 5,798,401, as well as in document WO 2007 / 058994 and by the applicant in patent application WO 2011 / 013073.

[0196] It is possible that, in the bituminous compositions and processes according to the invention, a single SBS block copolymer as described in the scope of the invention may be used, or that a mixture of SBS block copolymers as described in the scope of the invention may be used, or that one or more SBS block copolymers as described in the scope of the invention may be used in combination with one or more other elastomers. According to a preferred embodiment, the matrix is ​​made with only one or more, preferably a single, SBS elastomer. These elastomers preferably represent from 0.5% to 10% by mass, in particular from 1% to 6% by mass, and preferably from 1.5% to 4% by mass of the total mass of the bituminous composition. In the bituminous compositions according to the invention, said elastomer(s) is / are in a crosslinked form, but this does not affect the percentage that it / they represent within the composition.In other words, the percentages, before and after crosslinking, of the different components used for the preparation of the bituminous composition, are identical. When a mixture of elastomers, containing at least one elastomer other than the SBS elastomer as described in the context of the invention is used, the percentages of 0.5% to 10% in . The mass, in particular from 1% to 6% by mass, and preferably from 1.5% to 4% by mass, given in relation to the total mass of the bituminous composition, corresponds to the total quantity of elastomers used (SBS + other elastomer(s)). In this case of use of a mixture of elastomers, containing at least one elastomer other than SBS elastomers, the SBS elastomer represents at least 50%, preferably at least 70% by mass, and preferably at least 90% of the total quantity of elastomers used (SBS + other elastomer(s)).

[0197] Preferably, the SBS elastomer(s) represent at least 80% by mass of the total quantity of elastomers, preferably at least 90%, and preferably at least 95% of the total quantity of elastomers present, if a mixture of elastomers is used to prepare the bituminous compositions according to the invention. In particular, the mixture may contain a portion of S-B' used in the manufacture of the SBS elastomer by coupling, as explained above.

[0198] The bitumen / polymer composition (optionally crosslinked) according to the invention, preferably comprises from 0.1% to 20% by mass of elastomer, in particular of a copolymer of aromatic monovinyl hydrocarbon and conjugated diene, in particular of styrene and butadiene copolymer, relative to the mass of the bitumen / polymer composition (crosslinked).

[0199] According to one embodiment, the bitumen / polymer composition (optionally crosslinked) of the invention comprises from 1% to 8% by mass of elastomer, in particular of a copolymer of aromatic monovinyl hydrocarbon and conjugated diene, in particular of styrene and butadiene copolymer, relative to the mass of the crosslinked bitumen / polymer composition, more preferably from 2% to 5% by mass.

[0200] According to an alternative embodiment, the bitumen / polymer composition (optionally crosslinked) of the invention comprises from 5% to 20% by mass of elastomer, in particular of a copolymer of aromatic monovinyl hydrocarbon and conjugated diene, in particular of styrene and butadiene copolymer, relative to the mass of the crosslinked bitumen / polymer composition, more preferably from 10% to 15% by mass. Additives

[0201] According to one embodiment, the bituminous composition of the invention further comprises one or more additional additive(s).

[0202] These additional additives are known to those skilled in the art. By way of example, the following additives may be mentioned in particular:

[0203] a) the adhesion agents and / or surfactants. These are generally selected from alkylamine derivatives, alkylpolyamine derivatives, alkylamidopolyamine derivatives, and quaternary ammonium salt derivatives, taken alone or in mixtures. The quantity of adhesion agents and / or surfactants present in the bitumen / polymer composition is, for example, between 0.2% and 2% by weight, preferably between 0.5% and 1% by weight, relative to the total mass of the bitumen / polymer composition.

[0204] b) waxes of animal or vegetable origin or hydrocarbon waxes, in particular long-chain hydrocarbon waxes, for example polyethylene waxes or paraffins, optionally oxidized. Amide waxes, such as ethylene bis(stearamide), may also be added.

[0205] c) paraffins having chain lengths of 30 to 120 carbon atoms (C30 to C120). The paraffins are chosen from polyalkylenes. Preferably, the paraffins are polymethylene paraffins and polyethylene paraffins. These paraffins may be of petroleum origin or may come from the chemical industry. Preferably, the paraffins are synthetic paraffins resulting from the conversion of biomass and / or natural gas.

[0206] d) melting agents, such as oils based on animal and / or vegetable fatty substances or hydrocarbon oils of petroleum origin. The oils of animal and / or vegetable origin may be in the form of free fatty acids, triglycerides, diglycerides, monoglycerides or in esterified form, for example in the form of methyl ester.

[0207] e) anti-foam additives, in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes and fatty acid amides derived from vegetable or animal oils.

[0208] f) detergent additives and / or corrosion inhibitors, in particular (but not limited to) chosen from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkylpolyamines, polyetheramines and imidazolines.

[0209] g) sliding agents or anti-wear agents, in particular (but not limited to) selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glyceryl monooleate, and mono- and polycyclic carboxylic acid derivatives.

[0210] h) crystallization modifying additives, paraffin deposition inhibiting additives, pour point lowering additives; low temperature rheology modifiers, such as ethylene / vinyl acetate (EVA) and / or ethylene / vinyl propionate (EVP) copolymers, ethylene / vinyl acetate / vinyl versatate (EA / AA / EOVA) terpolymers; ethylene / vinyl acetate / alkyl acrylate terpolymers; graft-modified EVA copolymers; polyacrylates; acrylate / vinyl acetate / maleic anhydride terpolymers; amidated maleic anhydride / alkyl (meth)acrylate copolymers obtainable by reaction of a maleic anhydride / alkyl (meth)acrylate copolymer and an alkylamine or polyalkylamine having a hydrocarbon chain of 4 to 30 carbon atoms, preferably of 12 to 24 carbon atoms; amidated α-olefin / maleic anhydride copolymers capable of being obtained by reaction of an α-olefin / maleic anhydride copolymer and an alkylamine or polyalkylamine, the α-olefin being selectable from C10-C50 α-olefins, preferably C16-C20 α-olefins, and the alkylamine or polyalkylamine advantageously having a hydrocarbon chain of 4 to 30 carbon atoms, preferably of 12 to 24 carbon atoms.

[0211] i) antioxidants, for example of hindered phenolic type or amino type, of alkylated para-phenylenediamine type.

[0212] j) metal passivators.

[0213] k) acidity neutralizers.

[0214] 1) additives for lowering the mixing temperature of asphalts and coated, those allowing to improve the adhesion of bituminous binders to fillers and aggregates, such as, for example, polyisobutylene succinimides.

[0215] m) acids, such as polyphosphoric acid, or diacids, in particular fatty diacids.

[0216] Additives are used in quantities well known to those skilled in the art, depending on the nature of the additive, the bituminous base and the expected properties.

[0217] Preferably, when present, the content of additional additives varies from 0.1% to 10% by mass, preferably from 0.5% to 5% by mass, more preferably from 0.5% to 2.5% by mass, relative to the total mass of the bituminous composition of the invention. Composition

[0218] Advantageously, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably consists (exclusively of): - from 40% to 99.9% by mass of bitumen, - from 0.1% to 50% by mass of rosin ester(s), - from 0.1% to 30% by mass of plasticizing agent(s), - optionally, from 0.1% to 20% by mass of one or more elastomers, preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene, and - optionally, from 0.1% to 10% by mass of additional additive(s) as described above,

[0219] relative to the total mass of the bituminous composition.

[0220] According to a first embodiment, the bituminous composition of the invention comprises, preferably is made up essentially of, even more preferably is made up (exclusively): - from 50% to 99% by mass of bitumen, - from 0.5% to 30% by mass of rosin ester(s), - from 1% to 20% by mass of plasticizing agent(s), - optionally, from 1% to 8% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene - possibly, from 0.5% to 5% by mass of additional additive(s) as described above,

[0221] relative to the total mass of the bituminous composition.

[0222] Preferably, according to this first embodiment, the bituminous composition of the invention comprises, preferably is essentially constituted, even more preferably is (exclusively) constituted: - from 60% to 95% by mass of bitumen, - from 1% to 15% by mass of rosin ester, - from 2.5% to 10% by mass of plasticizing agent(s), and - optionally, from 2% to 5% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene - possibly, from 0.5% to 2.5% by mass of additional additive(s) as described above,

[0223] in relation to the total mass of the bituminous composition.

[0224] According to a second embodiment, the bituminous composition of the invention comprises, preferably consists essentially, even more preferably consists (exclusively): - from 50% to 99% by mass of bitumen, - from 0.5% to 30% by mass of rosin ester, - 1% to 20% by mass of plasticizing agent(s), and - possibly, from 5% to 20% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene - possibly, from 0.5% to 5% by mass of additional additive(s) as described above,

[0225] relative to the total mass of the bituminous composition.

[0226] Preferably, according to this second embodiment, the bituminous composition of the invention comprises, preferably consists essentially of, even more preferably is made up (exclusively): - from 60% to 95% by mass of bitumen, - 15% by mass of rosin ester, and - from 2.5% to 10% by mass of plasticizing agent(s), - optionally, from 10% to 15% by mass of one or more elastomer(s), preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene - possibly, from 0.5% to 2.5% by mass of additional additive(s) as described above,

[0227] relative to the total mass of the bituminous composition.

[0228] Preferably, the bituminous composition according to the invention is homogeneous. For "Homogeneous" means, in the sense of the invention, that the different components of the composition, namely the rosin ester(s), the plasticizing agent(s) and any elastomers and / or additives, are distributed uniformly in the bituminous matrix.

[0229] Preferably, the composition according to the invention has a penetrability at 25°C, measured according to standard EN 1426, ranging from 25 to 60 1 / 10 mm, more preferably from 30 to 50 1 / 10 mm.

[0230] Preferably, the composition according to the invention has a ball and ring softening temperature, measured according to standard EN 1427, greater than or equal to 55°C, more preferably greater than or equal to 60°C, advantageously ranging from 60°C to 80°C, typically ranging from 60°C to 75°C.

[0231] Preferably, the composition according to the invention has a threshold stress, measured according to standard NF EN 13587, less than or equal to 5 MPa, more preferably less than or equal to 3.5 MPa, advantageously ranging from 1 MPa to 5 MPa, typically ranging from 1.5 MPa to 3 MPa.

[0232] Preferably, the composition according to the invention has a maximum elongation stress, measured according to standard NF EN 13587, greater than or equal to 0.4 MPa, more preferably greater than or equal to 1 MPa, advantageously ranging from 0.4 MPa to 3 MPa, typically ranging from 0.8 MPa to 1.5 MPa.

[0233] Preferably, the composition according to the invention has a threshold elongation, measured according to standard NF EN 13587, greater than or equal to 5%, more preferably greater than or equal to 10%, typically between 8% and 15%.

[0234] Preferably, the composition according to the invention has a maximum elongation, measured according to standard NF EN 13587, greater than or equal to 500%, more preferably greater than or equal to 550%, even more advantageously greater than or equal to 600%, typically from 550% to 650%.

[0235] Preferably, the composition according to the invention has an energy at 400%, measured according to standard NF EN 13587, greater than or equal to 20 J / cm3, more preferably greater than or equal to 21 J / cm3, advantageously ranging from 20 J / cm3 to 50 J / cm3, typically ranging from 21 J / cm3 to 30 J / cm3.

[0236] Preferably, the composition according to the invention has a total energy, measured according to standard NF EN 13587, greater than or equal to 2.5 J, more preferably greater than or equal to 2.75 J, advantageously ranging from 2.5 J to 10 J, typically ranging from 2.75 J to 5 J.

[0237] According to one embodiment, the composition of the invention comprises a significant proportion of bio-sourced, recycled or waste-derived materials. It can therefore have a high eco-material index. The eco-material index is defined by the following equation:

[0238] Eco-material index = 100% - [% of non-biosourced, non-biodegradable, non-recycled or non-waste materials],

[0239] the percentages being expressed by mass, relative to the total mass of the composition.

[0240] According to one embodiment, the composition has an eco-material content of at least 5%, preferably at least 10%, preferentially at least 15%.

[0241] Advantageously, the bituminous composition of the invention has a content of biosourced compounds, measured according to standard ASTM D6866, greater than or equal to 5% by mass, relative to the total mass of the composition, preferably greater than or equal to 10% by mass, more preferably greater than or equal to 15% by mass.

[0242] For the purposes of this invention, "bio-based compound" means a material derived at least in part from biomass resources. Biomass resources are organic materials available on a renewable or recurring basis, such as crop residues, wood residues, grasses, and aquatic plants. Corn ethanol is a well-known example of a bio-based material derived from biomass resources.

[0243] The bio-based material content of a sample is typically determined by measuring the Carbon 14 (radioactive isotope of carbon) content present in said sample.

[0244] Indeed, the method defined in ASTM D6866 makes it possible to measure the traces of carbon-14 still present in a fossil. These traces of carbon-14 then make it possible to date the last time the molecules were absorbed (by ingestion or photosynthesis). This information is obtained thanks to the knowledge of the “half-life,” which is the time it takes for half the quantity of the isotope initially present to decay and disappear. This time is approximately 5700 years, meaning that every 5700 years, the quantity of carbon-14 decreases by half. It is also concluded that if a dead plant contains half as much carbon-14 as a living plant, it must have been alive 5700 years ago. years. Beyond 50,000 years, a sample contains virtually no trace of the original radioactive compound. If a laboratory analysis finds no remains in a fossil, the fossil is certainly over 50,000 years old. This is the case, for example, with oil and dinosaur bones.

[0245] Preferably, the bituminous composition of the invention has a carbon 14 content, measured according to ASTM D6866, greater than or equal to 3% by mass, relative to the total mass of the composition, preferably greater than or equal to 8% by mass, more preferably greater than or equal to 13% by mass.

[0246] Method for preparing a bituminous composition according to the invention

[0247] The bituminous compositions of the invention can be prepared by any process known to those skilled in the art. Generally, these processes include mixing the components and heating the resulting mixture. The bitumen may be heated before mixing. Usually, the bitumen is heated before mixing, and the additive(s) are added to the bitumen without having been preheated. According to a particular embodiment of the invention, a bitumen composition is prepared by bringing into contact:

[0248] - at least one bitumen base;

[0249] - at least one rosin ester, preferably as defined above;

[0250] - at least one plasticizing agent, preferably as defined above,

[0251] - possibly an elastomer as defined above;

[0252] - possibly one or more other additive(s), in particular one or more additional additive(s) as described above.

[0253] In particular, the following components are mixed under heating and stirring:

[0254] - at least one bitumen base,

[0255] - at least one rosin ester, preferably as defined above;

[0256] - at least one plasticizing agent, preferably as defined above,

[0257] - possibly an elastomer as defined above, chosen from among the copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene

[0258] - possibly one or more other additive(s), in particular one or more additional additive(s) as described above.

[0259] The mixture of the bitumen, the rosin ester, the plasticizing agent, or even the elastomer(s) and / or the other additive(s) present, can be carried out at a temperature ranging from 90°C to 230°C, preferably ranging from 120°C to 200°C, and preferentially ranging from 150°C to 180°C.

[0260] Such a mixture is produced with stirring, so as to facilitate the dispersion and good distribution of the rosin ester and the plasticizing agent, and possibly the elastomer, in the bitumen which will constitute the matrix of the composition, even typically in combination with the additional additive(s). The conditions are adapted to ensure a homogeneous mixture and the distribution of the rosin ester and the plasticizer (and elastomer). Typically, a person skilled in the art will adjust the stirring time and power, as well as the mixing temperature, particularly according to the type of bitumen, the precise nature of the rosin ester, the plasticizer, and the elastomer (if present) to obtain a molten mixture. Advantageously, the mixing is carried out in such a way as to promote good distribution of the rosin ester (and elastomer) in the final bituminous composition.

[0261] Generally, and as is known to those skilled in the art, the bitumen or mixture of bitumens used to manufacture the composition is preheated and stirred before the other constituents of the composition are incorporated. The incorporation of the rosin ester (and the elastomer) is generally carried out while the bitumen is maintained at a temperature in the range of 90 to 230°C, preferably in the range of 120 to 200°C, and preferably in the range of 150 to 180°C.

[0262] The constituents can be introduced simultaneously or sequentially. Heating is maintained throughout the process, and the heating temperature can be modulated during the process. Agitation can be maintained or interrupted intermittently as needed, or modulated during the process.

[0263] According to particular embodiments, the process according to the invention includes a homogenization step which allows, in particular, the distribution of the rosin ester (and the elastomer) in said composition. Such a step is in particular a mixing step of the different constituents, under agitation at a speed of 100 to 600 rpm, preferably 200 to 400 rpm and for a duration of 2 to 30 hours, preferably 6 to 24 hours, while the mixture is heated to a temperature in the range of 90 to 230°C, preferably in the range of 120 to 200°C, and preferably in the range of 150 to 180°C.

[0264] In the process according to the invention, one or more bitumens, one or more rosin esters, one or more plasticizing agents, optionally one or more elastomers, and even one or more additional additives, corresponding to the descriptions given previously in the relevant sections, are used. The crosslinked elastomers are introduced in a crosslinkable form into the compositions according to the invention and crosslinked in situ.

[0265] Of course, in the process, the quantities used of bitumen, rosin ester(s), plasticizing agent(s), or even elastomer(s) and / or additional additive(s) possibly present, will be adjusted by those skilled in the art to ultimately obtain the desired quantities in the final composition, and in particular those mentioned in the previous section relating to compositions according to the invention.

[0266] The characteristics described in the preceding sections also apply to the preparation processes according to the invention. Thus, the components involved in the preparation process will preferably be chosen from among those previously described and introduced in proportions that lead to the quantities given for the description of the bituminous compositions according to the invention.

[0267] Bituminous compositions that can be obtained by such processes also form an integral part of the invention. Applications

[0268] Various uses of the bituminous compositions according to the invention are envisaged. In particular, the bituminous compositions according to the invention can be used as a bituminous binder.

[0269] The bituminous binder or bituminous composition according to the invention can in turn be used to prepare an association with aggregates, in particular road aggregates. With regard to road applications, the invention relates in particular to bituminous coatings as materials for the construction and maintenance of road surfaces and their surfacing, as well as for carrying out all road works.

[0270] By bituminous coating is meant a mixture of a bituminous binder with aggregates and optionally mineral and / or synthetic fillers. The bituminous coating comprises a bituminous binder according to the invention, and optionally mineral and / or synthetic fillers, preferably chosen from fines, sand, gravel and recycled millings.

[0271] Aggregates are mineral and / or synthetic aggregates, in particular recycled millings, with dimensions greater than 2 mm, preferably between 2 mm and 20 mm.

[0272] The invention also relates to a method for preparing a bituminous coating comprising the hot mixing of a bituminous composition according to the invention, with aggregates, and optionally mineral and / or synthetic fillers.

[0273] The bituminous binder according to the invention can advantageously be used to prepare a surface dressing, hot mix asphalt, cold mix asphalt, cold-applied asphalt, or emulsion aggregate. With regard to road applications, the invention also relates to asphalts as materials for manufacturing and surfacing sidewalks.

[0274] By asphalt is meant a mixture of bituminous binder with mineral and / or synthetic fillers. An asphalt comprises a bituminous composition as described in the context of the invention and mineral fillers such as fines, sand or gravel and / or synthetic fillers. The mineral fillers are Asphalt consists of fines (particles smaller than 0.063 mm), sand (particles between 0.063 mm and 2 mm), and possibly gravel (particles larger than 2 mm, preferably between 2 mm and 4 mm). Asphalt has 100% compaction and is primarily used for constructing and surfacing sidewalks, while asphalt mixes have less than 100% compaction and are used for building roads. Unlike asphalt mixes, asphalt is not roller-compacted during installation.

[0275] The invention also relates to a process for preparing an asphalt comprising the hot mixing of a bituminous composition according to the invention, with mineral and / or synthetic fillers.

[0276] Another aspect of the invention relates to the use of a bituminous composition in various industrial applications, in particular for preparing a waterproofing coating, a membrane or an impregnation layer. As regards industrial applications of the bituminous compositions, mention may be made of the manufacture of waterproofing membranes, noise-reducing membranes, insulation membranes, surface coverings, carpet tiles, impregnation layers.

[0277] The invention also relates to the use of the combination of at least one rosin ester and at least one plasticizing agent, preferably as defined above, in a bituminous composition, preferably in an optionally crosslinked bitumen / polymer composition, to reduce the carbon footprint of said composition.

[0278] By "carbon footprint" of a product, is meant within the meaning of the invention the quantity of carbon (generally expressed in Kg of CO2 equivalent per Kg of product) necessary for the preparation of said product, this quantity of carbon equivalent taking into account both the consumption of energy, in particular linked to heating, and of raw materials. The carbon footprint of a product is typically determined according to any of the ISO 14040 and ISO 14044 standards.

[0279] Preferably, the use of a combination of at least one rosin ester and at least one plasticizing agent as defined above makes it possible to reduce the carbon footprint of a bituminous composition, in particular a bitumen / polymer composition (crosslinked or not), by at least 20% compared to the same composition free of rosin ester(s) and plasticizing agent as defined above, more preferably by at least 30%, even more preferably by at least 40%, advantageously by at least 80%, more advantageously by at least 90%, typically by at least 95%, for example by at least 98%. The values ​​expressed above are calculated assuming that the end-of-life bitumen is not burned and that the biogenic carbon present in the bitumen is not re-emitted.

[0280] The invention is illustrated by the following examples given by way of non-limiting example. EXAMPLES 1. Materials and methods

[0281] In the examples below, the bituminous compositions were evaluated according to the following protocols:

[0282] - the measurement of needle penetration at 25°C (abbreviation: P25), according to the standard EN 1426, the results being expressed in 1 / 10 mm,

[0283] - the measurement of the ring ball softening temperature (abbreviation: BBT), according to standard EN 1427, the results being expressed in °C,

[0284] - storage stability: the storage stability of concentrated compositions The above prepared composition is evaluated by measuring the difference in penetrability (APene) and the difference in TBA (ATBA) of each composition after 3 days of storage at 180°C.

[0285] - the elastic return at 25°C (R25), expressed as a percentage according to standard EN 13398,

[0286] - the mechanical properties (stress at maximum elongation, threshold elongation, maximum elongation, energy at 400%, total energy), measured according to standard NF EN 13587,

[0287] - the evaluation of the low temperature behavior of the compositions (BBR), according to standard EN 14771, by measuring the flexural rigidity modulus of the composition.

[0288] Raw materials

[0289] The compositions detailed below were prepared from the following raw materials:

[0290] Bitumen Base (B): grade 35 / 50 bitumen with a P25 penetrability of 40 1 / 10 mm and a TBA of 52°C, commercially available from TotalEnergies under the AZALT® brand.

[0291] SB S (E) thermocrosslinkable elastomer: styrene / butadiene / styrene (SBS) sequence copolymer, comprising 30.5% by mass of styrene and 69.5% by mass of butadiene. The content of pendant vinyl groups resulting from the 1,2-addition polymerization of butadiene is 27.8% by mass relative to the total mass of the copolymer. The copolymer has a weight-average molecular weight (Mw) of 142,500 Daltons and a polydispersity index (Ip) of 1.09. This copolymer is commercially available from KRATON under the name DI 192.

[0292] Rosin ester: product marketed by the company KRATON under the name: SYLVALITE® 2100 Rosin Ester. It is a resin of vegetable origin comprising a mixture of pentaerythritol esters of rosin and tall oil.

[0293] Plasticizing agent: tall oil pitch, commercially available from KRATON under the reference TALL OIL PITCH PN.

[0294] Crosslinking agent: sulfur-rich agent

[0295] Additive: additive for trapping hydrogen sulfide emissions (in English "H2S scavenger") 2. Preparation of binder compositions

[0296] Compositions Cl*, C2* and C3 are prepared according to the following protocol:

[0297] The pure bitumen is preheated to 160°C in an oven, then transferred to a 3L reactor in which it is heated for 1h at 180°C.

[0298] The elastomer, and optionally the rosin ester and the plasticizing agent, are then added and the mixture ground for 30 min at 6000 rpm, always at 180°C, using a high shear rotorstator (Silverson).

[0299] The reactor is then placed under mechanical stirring at 400 rpm for 2 hours at 180 °C.

[0300] Thus, the thermocrosslinked matrix of the bituminous composition is obtained.

[0301] The details of the compositions are given in Table 1 below. The contents are given by mass, relative to the total mass of the crosslinked bitumen / polymer composition.

[0302] [Tables 1] Cl* (comparative) C2* (comparative) C3 (according to the invention) Bitumen 96.81% 91.81% 86.64% Elastomer 3% 3% 3% Crosslinking agent 0.07% 0.07% 0.12% Additive 0.12% 0.12% 0.24% Rosin ester - 5% 5% Plasticizing agent - - 5%

[0303] The compositions Cl* and C2* are comparative.

[0304] Composition C3 is according to the invention. 3. Evaluations of binder compositions

[0305] The properties of compositions C1*, C2* and C3 were evaluated according to the protocols defined above. The results are summarized in Table 2 below.

[0306] [Tables2] Cl* (comparative) C2* (comparative) C3 (according to the invention) P25 (1 / 10 mm) 37 33 39 TBA (°C) 66.4 65.6 62.8 Elastic return at 25 °C (%) 85 80 82 Storage stability_3 days_180°C AP25 (1 / 10 mm) 1 1 1 ATBA (°C) 0.4 0.2 0 Energy evaluation at 400%, from yield stress at 5°C to maximum elongation (MPa) 1.01 1.40 1.20 Yield elongation (%) 11.68 10.18 9.79 Maximum elongation (%) 656 634 >700 Energy at 400% (J / cm2) 21.09 26.88 21.37 Total energy (in J) 3.86 5.48 4.69 BBR T°@S = 300MPa (°C) @60s -16 -14.8 -15.2 T° @ m = 0.300 (°C) @60s -17 -16.8 -17.1 m-value @ T @ S= 300MPa, 60s 0.319 0.320 0.327

[0307] It is observed that the Cl*, C2* and C3 compositions exhibit equivalent properties. In particular, the compositions all exhibit satisfactory properties, meeting the required technical specifications.

[0308] By comparing the results obtained for compositions Cl* and C2*, it is observed that the incorporation of rosin esters into the bitumen / polymer matrix leads to a slight decrease in penetration at 25°C, as well as in maximum elongation. However, these deteriorations in penetration at 25°C and maximum elongation are not observed in the context of composition C3 according to the invention, which further includes the plasticizing agent. In particular, composition C3, which incorporates both the rosin ester and the plasticizing agent, exhibits a penetration at 25°C and a maximum elongation greater than those of the reference Cl* composition.

[0309] It is also observed that composition C3 according to the invention has a 400% energy and a total energy significantly higher than those of composition Cl*. Composition C3 according to the invention thus has better resistance to deformation, compared to the reference composition Cl*. 4. Preparation and evaluation of bituminous mixtures

[0310] Compositions Cl* and C3 were used to prepare different bituminous mixes according to standards NF EN 12697-31 (PCG), NF P 298-51-1 (DURIEZ), NF EN 12 697-22 (rutting), NF EN 12697-26 (Module) and NF EN 12697-24 (Fatigue). One mix per binder composition to be evaluated and per test was thus prepared.

[0311] All the results obtained from the different coatings make it possible to verify that the binder compositions defined above do indeed meet the requirements of standard NF P98-130 relating to the preparation of bituminous coatings.

[0312] The results obtained are presented in the following table 3:

[0313] [Tables3] Test Specifications Cl* C3 PCG Void content at 60 gyrations (in %) between 5 and 10% 9.2 8.5 Duriez i / C ratio (wet / dry, in %) >70% 97 98.8 Rutting Rutting depth after 300 cycles (in %) <5% 2.01 2.55 Modulus Tensile-compression modulus, at 15°C, 10 Hz (in Mpa) >7000 11 372 12 107 Fatigue Relative deformation, 106 cycles at 10°C and 25 Hz (pdef) > 100 pdef 151 125

[0314] The results obtained conform to the required specifications: the Cl* and C3 compositions are both suitable for the preparation of bituminous mixes.

[0315] It should be noted, however, that composition C2 according to the invention leads to the preparation of asphalt mixes having a lower void content, compared to the asphalt mix prepared from composition Cl*. Composition C3 according to the invention would thus have improved workability compared to the comparative composition Cl*.

[0316] The DURIEZ test demonstrates that composition C3 according to the invention is insensitive to water. This property is surprising because a person skilled in the art would have expected that a composition incorporating 10% by mass of bio-based compounds would be sensitive to water.

[0317] Finally, it is noted that the C3 composition according to the invention has a higher modulus than the comparative Cl* composition: it therefore has better resistance to deformation.

Claims

Claims

1. Bituminous composition comprising: - at least one bitumen base, - at least one rosin ester, and - at least one plasticizing agent.

2. Bituminous composition according to claim 1, in which the plasticizing agent is chosen from: a) tall oil derivatives, b) plastic pyrolysis oils, c) triglycerides, d) mixtures of a) and / or b) and / or c).

3. A bituminous composition according to claim 1 or claim 2, wherein the rosin ester is selected from pentaerythritol esters of natural rosins, pentaerythritol esters of hydrogenated rosins and any mixture thereof, more preferably from pentaerythritol esters of natural rosins.

4. Bituminous composition according to any one of claims 1 to 3, in which said at least one rosin ester has a melting point, measured by differential scanning calorimetry, ranging from 40°C to 150°C, more preferably ranging from 50°C to 120°C.

5. Bituminous composition according to any one of claims 1 to 4, in which said at least one rosin ester has an acidity level, measured according to the ASTM D465 method, of less than or equal to 250 mg KOH / g, more preferably less than or equal to 100 mg of KOH / g

6. ë- Bituminous composition according to any one of the preceding claims, having a content of rosin ester(s) ranging from 0.1% to 50% by mass, preferably from 0.5% to 30% by mass, preferably from 1% to 15% by mass, relative to the total mass of the bituminous composition.

7. Bituminous composition according to any one of the preceding claims, further comprising at least one elastomer, preferably chosen from copolymers of a monovinyl aromatic hydrocarbon and a conjugated diene.

8. Crosslinked bitumen / polymer composition, obtained by crosslinking, in particular chemical or thermal, of a bituminous composition according to claim 7.

9. Process for preparing a bituminous composition according to any one of the preceding claims, this process comprising: 1) bringing the following components into contact: - at least one bitumen base, - at least one rosin ester, and - at least one plasticizing agent 2) mixing the components.

10. Preparation process according to claim 9, wherein the mixing of the components is carried out under heating and stirring, preferably at a temperature ranging from 90°C to 230°C, more preferably from 120°C to 200°C, even more preferably from 150°C to 180°C.

11. Use of a bituminous composition according to any one of claims 1 to 8, for preparing a surface coating, a hot mix, a cold mix, a cold-poured mix, a gravel emulsion or a wearing course, said binder being associated with aggregates and / or recycled millings.

12. Bituminous coating comprising a bituminous composition according to any one of claims 1 to 8, mixed with aggregates and / or recycled millings, and optionally mineral and / or synthetic fillers.

13. Asphalt comprising a bituminous composition according to any one of claims 1 to 8, in admixture with mineral and / or synthetic fillers.

14. A waterproofing coating, preferably a membrane or an impregnation layer, comprising a bituminous composition according to any one of claims 1 to 8.

15. Use in a bituminous composition, in particular in an optionally crosslinked bitumen / polymer composition, of the combination of at least one rosin ester and at least one plasticizing agent, to reduce the content of compound(s) of fossil origin in said composition.

16. Use in a bituminous composition, in particular in an optionally crosslinked bitumen / polymer composition, of the combination of at least one rosin ester and at least one plasticizing agent, to reduce the carbon footprint of said composition.